The structure of THF-coordinated [2,3,7,8,12,13,17, 18-octafluoro-5,10, 15,20-tetraphenylporphinato]zinc, Zn(F-8-TPP) THF, and photophysical studies of 2,3,7,8,12,13, 17,18-octafluoro-5, 10, 15,20-tetraphenylporphyrin, F8TPP, Zn(F8TPP), 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin F28TPP, and [2,3,7,8, 12,13,17,18-octafluoro-5,10, 15,20-tetrakis(pentafluorophenyl)porphinato]zinc Zn(F28TPP), in benzonitrile, are reported. A key point from these studies is that the octafluorinated F8TPP and perfluorinated F28TPP porphyrins possess similar absorption spectra, but dissimilar X-ray crystal structures and disparate photophysical characteristics. These data cannot be easily accommodated within currently accepted theories which relate macrocycle distortion and optoelectronic properties.